Le travail présenté dans cette thèse porte sur l'anode de la pile à combustible directe aux borohydrures (DBFC, selon l'acronyme anglais). Une première approche pour développer l'anode de la DBFC est d'étudier cette anode à l'intérieur du système global de la DBFC. Dans cette optique, des anodes composées des catalyseurs Pt/C et Pd/C ont été caractérisée en banc de test DBFC. D'autres facteurs ont aussi été étudiés, tels que la morphologie de l'anode et la stabilité des nanoparticules des catalyseurs.Le catalyseur d'anode de la DBFC doit idéalement exhiber une activité catalytique suffisante pour la réaction d'oxydation des borohydrures (BOR), tout en minimisant la production et l'échappement d'hydrogène gazeux durant la BOR. Ces aspects sont relativement difficiles à étudier en raison des nombreuses variables ne dépendant pas de l'anode dans un système DBFC réel. Une solution à ce problème consiste à isoler l'anode de la DBFC et de l'étudier en configuration demi-pile, avec un environnement d'étude mieux contrôlé. Les différentes méthodes pour évaluer un catalyseur d'anode de DBFC en demi-pile sont discutées, et des marqueurs sont proposés pour l'évaluation pertinente d'un catalyseur d'anode de DBFC par rapport aux résultats de la littérature.Une autre stratégie possible pour développer des catalyseurs adéquats d'anode de DBFC est de mieux comprendre le mécanisme de la BOR. Dans cette optique, la BOR est étudiée sur des électrodes modèles à base de platine. Chaque type d'électrode modèle permet de contrôler un paramètre précis de la surface catalytique, menant ainsi à différentes études de la BOR. La sensibilité de la BOR à la structure de surface catalytique est étudiée sur des électrodes massives de platine (polycristallin et monocristallin). L'empoisonnement de la surface active de Pt durant la BOR est étudié sur nanoparticules de Pt déposées sur substrat carbone vitreux plan. Des électrodes à trois dimensions ont également été réalisées : nanoparticules de Pt déposées sur nanofibres de carbone verticalement alignées. Le dépôt de différentes quantité de Pt a permis d'étudier l'influence de la densité en sites actifs de Pt sur la BOR. Les résultats obtenus sur ces électrodes modèles sont discutés avec ceux de la littérature, et un mécanisme pour la BOR sur Pt est proposé. Ce mécanisme est simulé en utilisant une modélisation de micro-cinétiques de type champs moyens. Les courbes simulées reproduisent les caractéristiques majeures des résultats expérimentaux. / The present work focuses on direct borohydride fuel cell (DBFC) anodes. A first approach to develop a suitable anode design for the DBFC consists in the study of the anode within the real DBFC system. In that frame, carbon-supported platinum and palladium nanoparticles are characterized and compared as anode electrocatalyst in DBFC configuration. Other variables such as the morphology of the anode and the stability of the catalyst nanoparticles are considered.The ideal DBFC anode catalyst should show a suitable electrocatalytic activity towards the borohydride oxidation reaction (BOR), without quantitative production/escape of gaseous hydrogen during the reaction. Studying these aspects is not straightforward using a real DBFC system, as the global behavior of the DBFC depends on numerous experimental variables external to the anode. In order to overcome this issue, a prospective anode catalyst can be isolated and specifically studied in half-cell configuration in a more controlled environment. The different methods possible for the evaluation of an electrocatalyst for the anode of the DBFC are discussed in this work, and benchmarks are proposed to compare a given material with the DBFC literature.Another strategy to develop suitable DBFC anode catalysts is to further understand the BOR mechanism. In that frame, the BOR is studied on model platinum-based electrodes with different levels of complexity. Bulk polycrystalline and single-crystals Pt flat electrodes enable to study the structure sensitivity of the BOR. The poisoning of the Pt active surface is investigated using Pt nanoparticles supported on flat glassy carbon substrate. Three-dimensional electrodes are also surveyed: Pt nanoparticles supported on vertically-aligned carbon nanofiber electrodes. The deposition of various amounts of Pt nanoparticles on the VACNF substrate enables to study the influence of the density of Pt active sites towards the BOR. The findings obtained using these model electrodes are gathered with previous results from the literature in order to propose a BOR mechanism on Pt. This mechanism is used in a mean-field microkinetics model. The simulated curves of this mechanism reproduce the main experimental features.

In recent years, electrochemical capacitors have emerged as devices with the potential to enable major advances in electrical energy storage. Electrochemical capacitors (ECs) are akin to conventional capacitors but employ higher surface-area electrodes and thinner dielectrics to achieve larger capacitances. This helps ECs to attain energy densities greater than those of conventional capacitors and power densities greater than those of batteries. Akin to conventional capacitors, ECs also have high cycle-lives and can be charged and discharged rapidly. But ECs are yet to match the energy densities of mid to high-end batteries and fuel cells. On the basis of mechanism involved in the charge-storage process, ECs are classified as electrical double-layer capacitors (EDLCs) or pseudocapacitors. Charge storage in EDLCs and pseudocapacitors is brought about by non-faradaic and faradaic processes, respectively. Faradaic process, such as an oxidation-reduction reaction, involves the transfer of charge between electrode and electrolyte. By contrast, a non-faradaic process does not use a chemical mechanism and charges are distributed on surfaces by physical processes that do not involve any chemical reaction. ECs employ both aqueous and non-aqueous electrolytes in either liquid or solid form, the latter providing the advantages of freedom from leakage of any liquid component, compactness, reliability and large operating potential-window. In the literature, polymer electrolytes are the most widely studied solid electrolytes. Complexation of functional-groups of certain polymers with cations results in the formation of polymer-cation complexes commonly referred to as solid-polymer electrolytes (SPEs). Mixing a polymer with an alkali metal salt dissolved in an organic solvent result in the formation of a polymer gel electrolyte. Organic solvents with low molecular-weights, such as ethylene carbonate and propylene carbonate, employed in polymer gel electrolytes are commonly referred to as plasticizers. When water is used as a plasticizer, the polymer electrolyte is called a polymer hydrogel electrolyte. Part I of the thesis is directed to studies pertaining to Polymer Hydrogel Electrolytes for Electrochemical Capacitors and comprises four sections. After a brief survey of literature on polymer hydrogel electrolytes employed in ECs in Section I.1, Section I.2 of Part I describes the studies on electrochemical capacitors employing cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration. Acidic poly (vinyl alcohol) hydrogel membrane electrolytes (PHMEs) with different perchloric acid concentrations are prepared by cross-linking poly (vinyl alcohol) with glutaraldehyde in the presence of a protonic acid acting as a catalyst under ambient conditions. PHMEs are characterized by scanning electron microscopy and temperature-modulated differential scanning calorimetry in conjunction with relevant electrochemical techniques. An optimised electrochemical capacitor assembled employing PHME in conjunction with black pearl carbon (BPC) electrodes yields a maximum specific capacitance value of about 96 F g-1, phase angle value of about 79o and a discharge capacitance value of about 88 F g-1. Section I.3 of Part I describes the studies on cross-linked poly (vinyl alcohol)/ploy (acrylic acid) blend hydrogel electrolytes for electrochemical capacitors. Acidic poly (vinyl alcohol)/poly (acrylic acid) blend hydrogel electrolytes (BHEs) have been prepared by cross-linking poly (vinyl alcohol)/poly (acrylic acid) blend with glutaraldehyde in presence of perchloric acid. These acidic BHEs have been treated suitably to realize alkaline and neutral BHEs. Thermal characteristics and glass-transition behavior of BHEs have been followed by differential scanning calorimetry. Ionic conduction in acidic BHEs has been found to take place by Grötthus-type mechanism while polymer segmental motion mechanism is predominantly responsible for ion motion in alkaline and neutral BHEs. Ionic conductivity of BHEs has been found to range between 10-3 and 10-2 S cm-1 at 298 K. Electrochemical capacitors assembled with acidic PVA hydrogel electrolyte yield a maximum specific capacitance of about 60 and 1000 F g-1 with BPC and RuOx.xH2O/C electrodes, respectively. Section I.4 of Part I describes the studies on gelatin hydrogel electrolytes and their application to electrochemical capacitors. Gelatin hydrogel electrolytes (GHEs) with varying NaCl concentrations have been prepared by cross-linking an aqueous solution of gelatin with aqueous glutaraldehyde under ambient conditions, and characterized by scanning electron microscopy, temperature-modulated differential scanning calorimetry, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic chronopotentiometry. Glass transition temperatures for GHEs range between 340 and 377 K depending on the dopant concentration. Ionic conductivity behavior of GHEs is studied with varying concentrations of gelatin, glutaraldehyde and NaCl, and conductivity values are found to vary between 10-3 and 10-1 S cm-1 under ambient conditions. GHEs have a potential window of about 1 V with BPC electrodes. The ionic conductivity of pristine and 0.25 N NaCl-doped GHEs follows Arrhenius behavior with activation energy values of 1.9×10-4 and 1.8×10-4 eV, respectively. Electrochemical capacitors employing GHEs in conjunction with black pearl carbon electrodes are assembled and studied. Optimal values for capacitance, phase angle, and relaxation time constant of about 81 F g-1, 75o, and 0.03 s are obtained for 3 M NaCl-doped GHE, respectively. EC with pristine GHE exhibits continuous cycle life for about 4.3 h as against 4.7 h for the electrochemical capacitor with 3 M NaCl-doped GHE. Unlike electrochemical capacitors, fuel cells do not store the charge internally but instead use a continuous supply of fuel from an external storage tank. Thus, fuel cells have the potential to solve the most challenging problem associated with the electrochemical capacitors, namely their limited energy-density. A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided with fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and potable water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in various laboratories but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid-Polymer-Electrolyte-Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient-temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen with some content of carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed / liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol, and diethyl ether have been considered for fuelling PEFCs directly. Among these, methanol with a hydrogen content of about 13 wt. % (specific energy = 6.1 kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the cell performance during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride, which has a hydrogen content of about 11 wt. %. Such fuel cells are called direct borohydride fuel cells (DBFCs). Part II of the thesis includes studies on direct borohydride fuel cells and comprises three sections. After a brief introduction to DBFCs in section II.1, Section II.2 describes studies on an alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant. A peak power density of about 150 mW cm-2 at a cell voltage of 540 mV could be achieved from the optimized DBFC operating at 70oC. Section II.3 describes studies on poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells. This DBFC employs a poly (vinyl alcohol) hydrogel membrane as electrolyte, an AB5 Misch metal alloy as anode, and a gold-plated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. The performance of the PHME-based DBFC in respect of peak power outputs, ex-situ cross-over of oxidant, fuel, anolyte and catholyte across the membrane electrolytes, utilization efficiencies of fuel and oxidant as also cell performance durability under ambient conditions are compared with a similar DBFC employing a Nafion®-117 membrane electrolyte (NME). Peak power densities of about 30 and 40 mW cm-2 are observed for the DBFCs with PHME and NME, respectively. The PHME and NME-based DBFCs exhibit cell potentials of about 1.2 and 1.4 V, respectively, at a load current density of 10 mA cm-2 for 100 h. Publications of Nurul Alam Choudhury 1. Gelatin hydrogel electrolytes and their application to electrochemical supercapacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Electrochem. Soc., 155 (2008) A74. 2. Cross-linked polymer hydrogel electrolytes for electrochemical capacitors, N. A. Choudhury, A. K. Shukla, S. Sampath, and S. Pitchumani, J. Electrochem. Soc., 153 (2006) A614. 3. Hydrogel-polymer electrolytes for electrochemical capacitors: an overview, N. A. Choudhury, S. Sampath, and A. K. Shukla, Energy and Environmental Science (In Press). 4. Cross-linked poly (vinyl alcohol) hydrogel membrane electrolytes with varying perchloric acid dopant concentration and their application to electrochemical capacitors, N. A. Choudhury, S. Sampath, and A. K. Shukla, J. Chem. Sc. (Submitted) 5. An alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant, N. A. Choudhury, R. K. Raman, S. Sampath, and A. K. Shukla, J. Power Sources, 143 (2005) 1. 6. Poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells, N. A. Choudhury, S. K. Prashant, S. Pitchumani, P. Sridhar, and A. K. Shukla, J. Chem. Sc. (Submitted). 7. A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes, G. Selvarani, A. K. Sahu, N. A. Choudhury, P. Sridhar, S. Pitchumani, and A. K. Shukla, Electrochim. Acta, 52 (2007) 4871. 8. A high-output voltage direct borohydride fuel cell, R. K. Raman, N. A. Choudhury, and A. K. Shukla, Electrochem. Solid-State Lett., 7 (2004) A 488. 9. Carbon-supported Pt-Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells, A. K. Shukla, R. K. Raman, N. A. Choudhury, K. R. Priolkar, P. R. Sarode, S. Emura, and R. Kumashiro, J. Electroanal. Chem., 563 (2004) 181.

La pile à combustible directe à borohydrures (DBFC en anglais), qui est une sous-catégorie des piles à combustible alcalines, bénéficie des avantages de son combustible, le borohydrure de sodium (NaBH4), qui confère à ce système des caractéristiques thermodynamiques et énergétiques très intéressantes. Cependant, la réaction d’électrooxydation de NaBH4 (BOR en anglais) est très complexe et reste à ce jour encore peu étudiée et mal comprise sur la majorité des électrocatalyseurs (la plupart étant sous forme de nanoparticules métalliques supportées sur des noirs de carbone). De plus, de récentes études ont montré l’agressivité du milieu alcalin sur la durabilité des électrocatalyseurs conventionnels, révélant une grande perte de surface catalytique active, due principalement à un détachement des nanoparticules du support carboné. Dans ce contexte, ces travaux de thèse se sont orientés vers trois axes d’étude : (i) l’étude de la BOR sur des électrocatalyseurs à base de palladium dans des conditions proches des conditions réelles de fonctionnement de la DBFC ; (ii) l’étude de l’impact de la structure de l’anode sur les performances globales de la DBFC, et (iii) l’étude du mécanisme de dégradation d’électrocatalyseurs à base de métaux nobles dans un environnement alcalin. Les expérimentations ont été réalisées en étroite collaboration avec le U.S. Naval Research Laboratory (Washington, USA).Les résultats obtenus ont montré qu’une grande concentration en NaBH4 entraine un ralentissement de la cinétique de la réaction, due en partie à un fort empoisonnement de la surface catalytique. Par ailleurs, des marqueurs d’activité pour la BOR ont été proposés. Ensuite, l’utilisation d’électrodes à gradient de catalyseurs s’est avérée être une solution prometteuse pour mieux valoriser l’hydrogène produit via des réactions secondaires à la BOR. Enfin, l’utilisation de la spectroscopie infrarouge à transformée de Fourier couplée à de la microscopie électronique en transmission à localisation identique a permis de détecter la formation de carbonates au cours d’un test de vieillissement accéléré d’électrocatalyseurs à base de métaux nobles en milieu alcalin. Ce mécanisme explique, en partie, le détachement des nanoparticules observé au cours du test. / The direct borohydride fuel cell (DBFC), a subclass of alkaline fuel cells, benefits from the advantages of its fuel, sodium borohydride (NaBH4), which exhibits very interesting thermodynamic and energetic characteristics. However, the NaBH4 electrooxidation reaction (BOR) is very complex; to date it remains poorly studied and understood on many electrocatalysts (most of them are in the form of metal nanoparticles supported on carbon black). In addition, recent studies reported the aggressiveness of the alkaline medium on the durability of conventional carbon-supported electrocatalysts, revealing a large loss of the active catalytic surface, mainly due to the detachment of nanoparticles from the carbon support. In this context, this thesis focused on three main areas of study: (i) the study of the BOR on palladium-based electrocatalysts in conditions close to the real operating conditions of the DBFC; (ii) the study of the impact of the anode structure on the overall performance of the DBFC, and (iii) the study of the degradation mechanism of noble metal electrocatalysts in alkaline environment. The experiments were carried out in close collaboration with the U.S. Naval Research Laboratory (Washington, USA).The results obtained showed that a high concentration of NaBH4 leads to a decrease of the reaction kinetics, due in part to poisoning of the catalytic surface. In addition, activity markers for the BOR have been proposed. Then, the use of catalysts-gradient electrodes proved to be a promising solution to better valorize the hydrogen produced via side reactions of the BOR. Finally, the use of Fourier transform infrared spectroscopy coupled with identical-location transmission electron microscopy enabled to detect the formation of carbonates during the accelerated stress test of carbon-supported noble metal electrocatalysts in alkaline medium, explaining, in part, the detachment of nanoparticles observed during the test.

Drei Wasserstoffgenerator-Systeme (WGS) auf Basis chemischer Hydride wurden in dieser Arbeit als Labormuster ausgelegt, gefertigt und in ihren Betriebseigenschaften analysiert. Es wurden ein 20 W-WGS und zwei 100 W-WGS untersucht. Als chemische Hydride wurden Amminboran und Natriumborhydrid ausgewählt. Aufgrund ihrer vergleichsweise einfachen Lagerfähigkeit, ihren moderaten Freisetzungsbedingungen und ihrer volumetrisch wie gravimetrisch hohen Wasserstoffdichten erschienen sie in besonderer Weise geeignet für Wasserstoffgeneratoren im Kleinleistungsbereich. Zwar zeigen diese chemischen Hydride zurzeit hinsichtlich ihrer Kosten, ihrer Energieeffizienz bei der Herstellung und ihrer Umweltverträglichkeit keine Vorteile gegenüber verdichtetem Wasserstoff, jedoch besitzen sie mit ihrer hohen, auf das Hydrid bezogenen Energiedichte ein positives Alleinstellungsmerkmal. Bei der Entwicklung der WGS standen daher neben der Betriebszuverlässigkeit und Regelbarkeit die Optimierung der systembezogenen Energiedichte WGS im Fokus.:Versicherung Inhaltsverzeichnis Abkürzungsverzeichnis 1 Einleitung 2 Grundlagen1 2.1 Aufbau eines Wasserstoffgenerator-Systems 2.2 Anforderungen an das Wasserstoffgenerator-System 2.2.1 Anwendungsspezifische Anforderungen 2.2.2 Brennstoffzellenspezifische Anforderungen 2.3 Auswahl der Wasserstoffquelle 2.3.1 Reversible Wasserstoffquellen 2.3.2 Irreversible Wasserstoffquellen 2.4 Auslegung der Subsysteme 2.4.1 Auslegung des Vorratssystems 2.4.2 Auslegung des Reaktors 2.4.3 Auslegung des Aufbereitungssystems 3 Wasserstoffgenerator zur Amminboran-Thermolyse 3.1 Thermolyse von Amminboran in Triglyme 3.2 Systemspezifikationen 3.3 Untersuchungen der Wasserstoffquelle 3.3.1 Konzentrationsabhänigkeit der Thermolysereaktion 3.3.2 Der Mechanismus der H2-Freisetzung 3.3.3 Temperaturabhängigkeit der Thermolysereaktion 3.4 Systemkonzeption und Reaktorauslegung 3.5 Charakterisierung und Diskussion 3.5.1 Thermische Analyse 3.5.2 Betriebsverhalten 3.5.3 Energiedichte des Wasserstoffgenerator-Systems 3.6 Fazit zum Amminboran-Thermolyse basierten System 4 Wasserstoffgenerator zur Amminboran-Hydrolyse 4.1 Wasserstofferzeugung durch Amminboran-Hydrolyse 4.2 Systemspezifikationen 4.3 Untersuchungen der Wasserstoffquelle 4.3.1 Die Säure der Wasserstoffquelle 4.3.2 Reaktionskinetik der Wasserstoffquelle 4.3.3 Umsatz und Energiedichte der Wasserstoffquelle 4.4 Systemkonzept und Reaktorauslegung 4.4.1 Systemkonzept 4.4.2 Reaktorauslegung 4.4.3 Reaktorkonstruktion 4.5 Charakterisierung und Diskussion 4.5.1 Betriebsverhalten 4.5.2 Thermische Analyse 4.5.3 Energiedichte des Wasserstoffgenerator-Systems 4.5.4 Gasanalyse 4.6 Fazit zu AB-Hydrolyse basierten WGS 5 Wasserstoffgenerator zur Natriumborhydrid-Hydrolyse 5.1 Wasserstofferzeugung durch Natriumborhydrid-Hydrolyse 5.2 Systemspezifikationen 5.3 Untersuchung der Wasserstoffquelle 5.3.1 Die Säure der Wasserstoffquelle 5.3.2 Lagerfähigkeit der Wasserstoffquelle 5.3.3 Umsatz und Energiedichte der Wasserstoffquelle 5.4 Systemkonzept und Reaktorauslegung 5.5 Charakterisierung und Diskussion 5.5.1 Betriebsverhalten 5.5.2 Thermische Analyse 5.5.3 Energiedichte des Wasserstoffgenerator-Systems 5.6 Fazit zu Natriumborhydrid basierten Wasserstoffgenerator- Systemen 6 Zusammenfassung 7 Ausblick Anhang A1 Ergänzende Informationen zu den Grundlagen A2 Ergänzende Informationen zum Wasserstoffgenerator-System zur Amminboran-Thermolyse A3 Ergänzende Informationen zur Auswahl des Systemkonzeptes des Wasserstoffgenerator-Systems zur Amminboran-Hydrolyse A3.1 Bewertungskategorien und ihre Gewichtung A3.2 Einzelbewertungen der Systemkonzepte zur AB-Hydrolyse A4 Berechnungsgrundlagen der Reaktorkonstruktion zur Amminboran-Hydrolyse A5 Experimentelle Parameter und Daten zur thermischen Analyse des Reaktors zur Amminboran-Hydrolyse A.6 Ergänzende Informationen zum Wasserstoffgenerator-System zur Hydrolyse von festem Natriumborhydrid A6.1 Untersuchung der Wasserstoffquelle A6.2 Systemkonzept und Reaktorauslegung A6.3 Charakterisierung und Diskussion Abbildungsverzeichnis Tabellenverzeichnis Literaturverzeichnis Publikationen